Antistatic fiber containing chain-extended tetrols based on diamines

ABSTRACT

It has been suggested that antistatic properties of fibers of polyamide could be improved by dispersing in the polyamide a small proportion of a reaction product of a tetrol compound represented by the formula:   WHERE A, B, C, D, E, F, G, AND H ARE EACH A WHOLE NUMBER AND A is a difunctional radical from a hydrocarbon containing 1 to 13 carbon atoms, said tetrol compound having a molecular weight between about 4,000 and about 50,000, and at least one compound selected from the group consisting of diepoxides and compounds which yield the following divalent radicals:   WHERE A&#39;&#39; is a difunctional radical from a hydrocarbon containing 1 to 30 carbon atoms. However, with incorporation of this antistatic additive in the polyamide, serious problems have been encountered in meltspinning due to the frequent occurrence of &#39;&#39;&#39;&#39;nubs&#39;&#39;&#39;&#39; or enlarged places in the extruded polyamide filament. It has now been found that the occurrence of said nubs in the antistatic polyamide fiber can be greatly reduced by dispersing in the polymer an additional small proportion of a hindered phenol represented by the formulae:   IN WHICH X HAS A VALUE OF FROM 1 TO 6 AND Y HAS A VALUE OF FROM 6 TO 30; AND   IN WHICH R is   WHEREIN X&#39;&#39; HAS A VALUE FROM 1 TO 6 AND Y&#39;&#39; HAS A VALUE OF 1 TO 6. When the term &#39;&#39;&#39;&#39;alkyl&#39;&#39;&#39;&#39; is qualified by the designation &#39;&#39;&#39;&#39;(lower),&#39;&#39;&#39;&#39; there is intended a branched or straight chain hydrocarbon of from 1 to about 6 carbon atoms. Preferably, the phenol compound is used with at least 0.1% by weight, based on the weight of the antistatic additive, of a sulfur compound of the formula:   WHEREIN R&#39;&#39;&#39;&#39; is an alkyl radical containing 8 to 18 carbon atoms and n is 1 to 3.

United States Patent [191 Crescentini et al.

[4 1 June 3,1975

[ ANTISTATIC FIBER CONTAINING CHAIN-EXTENDED TETROLS BASED ON DIAMINES[75] Inventors: Lamberto Crescentini; Rodney Lee Wells, both of Chester,Va.

Allied Chemical Corporation, New York, NY.

221 Filed: Aug. 5, 1974 211 Appl. No.: 494,421

Related US. Application Data [62] Division of Ser. No. 271,316, July 12,1972.

[73] Assignee:

[51] Int. Cl. C08G 41/04 [58] Field of Search 260/830 P, 857 PG, 45.85B, 260/45.85 S

[5 6] References Cited UNITED STATES PATENTS 3,285,855 11/1966 Dexter 1260/45.85 S

3,330,859 7/1967 Dexter 260/45.85 B 3,364,250 1/1968 Dexter 260/45.85 B3,594,448 7/1971 Birenzvige... 260/45.85 B 3,657,386 4/1972 Weedon260/857 PG 3,723,489 3/1973 Dexter 260/45.85 B 3,723,503 3/1973 Dexter260/45.85 B 3,772,403 11/1973 Wells.. 260/857 PG 3,787,523 1/1974Crescentin 260/857 PG Primary ExaminerPaul Lieberman Attorney, Agent, orFirmFred L. Kelly 57 ABSTRACT It has been suggested that antistaticproperties of fibers of polyamide could be improved by dispersing in thepolyamide a small proportion of a reaction product of a tetrol compoundrepresented by the formula:

where A is a difunctional radical from a hydrocarbon containing 1 to 30carbon atoms.

However, with incorporation of this antistatic additive in thepolyamide, serious problems have been encountered in melt-spinning dueto the frequent occurrence of nubs or enlarged places in the extrudedpolyamide filament. It has now been found that the occurrence of saidnubs in the antistatic polyamide fiber can be greatly reduced bydispersing in the polymer an additional small proportion of a hinderedphenol represented by the formulae:

(lower) alkyl (lower) alkyl in which x has a value of from 1 to 6 and yhas a value of from 6 to 30; and

(CH2) X ,c0- (CH2) 5,

(lower) 'alkyl wherein x has a value from 1 to 6 and y' has a value of 1to 6.

When the term alkyl is qualified by the designation (lower), there isintended a branched or straight cu I Moon CH (OCHCH (ca cao) (ca ca o)1H 2 o 2 c o 2 2 a r N/ ca I chain hydrocarbon of from 1 to about 6carbon atoms.

Preferably, the phenol compound is used with at least 0.1% by weight,based on the weight of the antistatic additive, of a sulfur compound ofthe formula:

n (c a COOR COOR wherein R" is an alkyl radical containing 8 to 18carbon atoms and n is 1 to 3.

10 Claims, No Drawings ANTISTATIC FIBER CONTAINING 'orientable substancewhich interferes with normal fiber CHAIN-EXTENDED TE ROLS ASE O stretchin a short section, resulting in an enlargement.

DIAMINES Foreign substances which are believed to have contributed tonubs in the present instance include carbonized 5 polymer from face ofextruder die and spinnerette, and iaii f fi gg RELATED gels formed inthe polymer. Gels appear to be the chief cause, i.e., the nubs areprobably created by non- This is a division, of Application Sen 271,316,orientable gel from cross-linked polymer. Thermal degfiled July 12,1972. radation of the polymer may be an important causative Thisapplication is directed to an improvement upon factor the inventiondisclosed in US. Application Ser. No. The reactions in thermaldegradation of polyamides filed 31, 1972- Application Sen containingpolyalkylene ether additives are not entirely 239905 is herebyincorporated y reference into this understood. It is likely that thermaldegradation proapplication. duces a decomposition product which servesto form cross-links between amide groups and adjacent poly- BACKGROUNDOF THE INVENTION mer chains. The decomposition reaction proceeds Thisinvention elates o a PYOCeSS for the meltslowly, finally buildingupathree-dimensional network spinning of a filamentary structure from asynthetic of molecules hi h may b ll d polymer l d polyamide p y Morepaiticiiiariy it is concerned which eventually'reaches the stage whereit forms an With an iinpioveci process for the formation of an infusiblecoating on the walls of the reactor and other proved antistaticfilament, yarn or the like by meltequipment pinni g synthetic linealfiber-forming p y A serious difficulty which arises from the formationit has been suggested that the utility of synthetic of this polymer gelon the interior walls is that from bers could be increased and theirproperties, in particui to i pieces b k ff d t i t h fl i lar theirantistatic properties, could be improved if a polymer stream where th de damage to the polyalkylene ether of high molecular weight is includedi i equipment,

in the polymer. More specifically, it is disclosed in US. The greatestdifficulty, however, is caused by polya 3,475,898 to Magat and Sharkeyto use mer gel which has progressed to the three-dimensional p yl y p pygiycois for this p p structural stage, but which has not yet reached theMore r y. 3,657,386 discloses that stage of being infusible. This kindof polymer gel is certain propylene oxide-ethylene Oxide copolymersreadily carried with the stream of flowing polymer. based on ethylenediamine are useful in preparation of Being still molten or at leastsoftened, it passes through an antistatic fiber of polyamide. It hasalso been sugh pump d even th h the filter medium to'show gested thatthe utility of synthetic fiber of P yf up either as discontinuities oras viscosity differences in could be increased by dlspersmg In tpolyamlde an the spun filament. When these filaments are later coldantistatic compound which is a reaction product of: drawn, thesedefects-may cause breaks in the filaments 2CH0) g (CIIZCHZO) H where a,b, c, d, e, f, g, and h are each a whole number which either cause thewhole thread to break or else and A is a difunctional radical from ahydrocarbon conform nubs which go through to be counted as qualitytaining l to 13 carbon atoms, said tetrol compound defects in the finalyarns.

having a molecular weight between about 4,000 and about 50,000, and atleast one compound selected from SUMMARY OF THE iNVENTiON the groupconsisting of diepoxides and compounds which yield the followingdivalent radicals:

It is an object of this invention to avoid the above difficulties byminimizing gel formations in the molten O O polyamide. Another object isto avoid accumulation of u polymer gel on the walls of the reactor, inthe pump, or nd in the filtering medium when melt-spinning thepolyamide. A further object is to improve the uniformity and 9 H H 0quality of filaments or fibers formed from the molten polymer, inparticular to minimize nub formation in the filaments. Other objectswill become apparent from the where A is a difunctional radical from ahydrocarbon 6O disclosure and the pp claimscontaining 1 to 30 carbonatoms. However, with use of These objects are accomplished by thepresent inventhis antistatic agent, serious problems were encountionwhich provides an improvement in the process for tered in melt-spinningdue to the frequent occurrence the formation of an antistatic polyamidefiber from a of nubs in the fiber. The term nubs isconventionfiber-forming polyamide polymer containing about 1 allyapplied and is used herein to mean enlarged secpercent to 12 percent byweight of an antistatic comtions of filament no more than severalfilament diamepound which is a reaction product of a tetrol comters inlength. Nubs may be formed by a foreign, nonpound represented by theformula:

H (OCH CH (OCHCH H (OCH2CH2) f where a, b, c, d, e,f, g, and h are eacha whole number and A is a difunctional radical from a hydrocarboncontaining l to 13 carbon atoms, said tetra] compound having a molecularweight between about 4,000 and about 50,000 and at least one compoundselected from the group consisting of diepoxides and compounds whichyield the following divalent radicals:

II II ocnca where A is a difunctional radical from a hydrocarboncontaining 1 to 30 carbon atoms, by extruding the molten polymer throughan orifice into a quenching medium and thereafter stretching theresulting filaments, the improvement comprising dissolving in theextrudate prior to extrusion at least 0.1 percent by weight, preferably0.5 to 8 percent, based on the weight of the antistatic compound, of aphenol of the formulae:

(lower) alkyl (lower) alkyl in which x has a value of from 1 to 6 and yhas a value of from 6 to 30; and

wherein X has a value from 1 to 6 and y has a value of 1 to 6.

When the term alkyl" is qualified by the designation (1ower)," there isintended a branched or straight chain hydrocarbon of from 1 to 6 carbonatoms Preferably, the phenol compound is used with at least 0.1% byweight, based on the weight of the antistatic additive, of a sulfurcompound of the formula:

(CH CHO) C (CH CH O) (CHZCHO) g (CH CH O) 1-I wherein R" is an alkylradical containing 8 to 18 carbon atoms and n is l to 3.

As stated above, the present invention is an improvement upon theinvention disclosed in U.S. Application Ser, No. 239,905 which relatesto an antistatic fiber containing a novel antistatic compound. The novelantistatic compound is prepared by reacting a tetrol compound, asdescribed above, with a chain-extender compound, for example adiepoxide, a dicarboxylic acid or dialkyl ester thereof, or adiisocyanate, to form predominantly branched, chain-extended polymerhaving a melt viscosity of about 800 to 50,000 centipoises, preferably1,500 to 25,000 centipoises, at 100C. Preferably, the ethylene oxidemoiety makes up 10 to of the molecular weight of the antistaticcompound. The mol ratio of chain-extender compound to tetrol compound ispreferably between about 0.7 and 1.0.

The alkylated phenol compounds useful in the present invention are knowncompounds and some are commercially available. The alkylation of phenolsis readily conducted with a variety of catalysts and alkylating agents;see Price, Organic Reactions III, 58 (1946). The preparation of2,6dialkylphenols by direct alkylation is relatively difficult but aprocedure is furnished in Journal of Organic Chemistry, 21, 712 (1956).Pertinent patents include U.S. Pat. No. 3,285,855 and U.S. Pat. No.3,330,859. The sulfur compounds of the invention may be prepared inaccordance with Chemical Abstracts, 64, 3362C. U.S. Patent 2,762,836 isalso pertinent.

The tetrol compound which is chain-extended for use as an antistaticadditive in this invention is fully described in U.S. Pat. No. 2,979,528to Lundsted, assignor to Wyandotte. Suitable tetrol compounds arecommercialy available under the trademark Tetronic as a series ofpoly(oxyethylene)-poly(oxypropylene) block copolymers having molecularweights from 1,650 to over 26,000. This series varies in length ofpoly(oxyethylene) chain and poly(oxypropylene) chain. A 3 and 4 digitcode number indicates the molecular composition. When four digits areemployed, the first two explain the average molecular weight of thehydrophobe (poly(oxypropylene) branches on the alkylenediamine). Whenthree digits are used only the first number serves this purpose. Thelast digit of each code number represents the weight percentage ofhydro- COOR" philic (poly(oxyethylene)) units to the nearest 10%..

The tetrol compounds in the examples are described this way.

As diamines upon which the tetrols are based, in addition to ethylenediamine, diamines of a hydrocarbon containing 1 to 13 carbon atoms,preferably the lower alkyl diamines, where the lower alkyl radicalcontains 1-6 carbon atoms, can be used.

extend the tetrols based on diamines, are those polyepoxy compoundsdescribed in British specification No. 793,915 to Union Carbide on page2, line 48 to line 121.

Also useful to form chain-extending divalent radicals are the aromaticor aliphatic diisocyanates, having a structure OCNA'NCO, where A isdefined as above.

The antistatic fiber of this invention may also contain conventionalfiber additives such as antioxidants, stabilizers, delusterants, dyeingassists, and colorants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention will now befurther described in the following specific examples which are to beregarded solely as illustrative and not as restricting the scope of theinvention.

EXAMPLE 1 This example shows a method of preparing a preferredantistatic additive of the type disclosed in U.S.

CHCH O Three-hundred grams of Tetronic 1504 (molecular weight 12,500)was placed in a three-neck flask fitted with a thermometer, stirrer, andaddition funnel. The Tetronic 1504 was stirred and heated to 100C. and5.7 grams of 4,4 methylene bis (cyclohexyl) isocyanate,

(molecular weight 262.4) was added dropwise to the material in theflask. Agitation was continued for one hour at 100105C. after theaddition was completed. Then the product was cooled to room temperature.It was a soft solid having a melt viscosity of 8,300 centipoises at100C. measured with the Brookfield viscometer. The viscosity of theoriginal Tetronic 1504 was 200 centipoises at 100C.

EXAMPLE 3 This example shows a method of preparing a preferredantistatic additive of the type disclosed in U.S. Application Ser. No.239,905 filed Mar. 31, 1972. The instant chainextended polymer isprepared from a tetrol compound covered by U.S. Pat. No. 2,979,528 toLundsted, and sold commercially as Tetronic 1504.

Three hundred grams of Tetronic 1504(molecular weight 12,500) was placedin a three-neck flask fitted with a thermometer, stirrer, and additionfunnel. The Tetronic 1504 was stirred and heated to 105C., and

7.4 grams of diglycidyl ether of 2,2-bis(4 -hydroxyphenyl)-propane ofthe structure:

Application Ser. No. 239,905, filed Mar. 31, 1972. The (molecular weight340.4) was added to the material in instant chainextended polymer isprepared from a tetrol compound covered by U.S. Pat. No. 2,979,528 toLundsted, and sold commercially as Tetronic 1504.

Three hundred grams of Tetronic 1504 (molecular weight 12,500) wasplaced in a three-neck flask fitted with a thermometer, stirrer, andaddition funnel. The Tetronic 1504 was stirred and heated to 105C, and4.2 grams of dimethyl terephthalate (molecular weight 194.2) was addedto the material in the flask. Agitation was continued for 3.25 hours at200C. after the addition was completed. Then the product was cooled toroom temperature. It was a soft solid having a melt viscosity of 13,820centipoises at 100C., measured with the Brookfield viscometer. Theviscosity of the original Tetronic 1504 was 200 centipoises at 100C.

EXAMPLE 2 This example shows a method of preparing a preferredantistatic additive of the type disclosed in U.S. Application Ser. No.239,905, filed Mar. 31, 1972. The instant chain-extended polymer isprepared from a tetrol compound covered by U.S. Pat. No. 2,979,528 toLundsted, and sold commercially as Tetronic 1504.

the flask. Agitation was continued for 2.5 hours at 190C. after theaddition was completed. Then the product was cooled to room temperature.It was a soft solid having a melt viscosity of 6,000 centipoises at100C. measured with the Brookfield viscometer. The viscosity of theoriginal Tetronic 1504 was 200 centipoises at 100C.

EXAMPLE 4 A glass reactor equipped with a heater and stirrer was chargedwith a mixture of 1,520 grams of ecaprolactam and grams of aminocaproicacid. The mixture was then flushed with nitrogen and was stirred andheated to 255C. over a 1 hour period at atmospheric pressure to producea polymerization reaction. The heating and stirring was continued atatmospheric pressure under a nitrogen sweep for an additional 4 hours inorder to complete the polymerization. During the last 30 minutes of thepolymerization, 2.7 grams of tetra[methylene 3-( 3 ',5'-di-tertiary-butyl-4-hydroxyphenyl)propionatelmethane and grams of theantistatic compound of Example 1, were added to the polycaproamide andstirring was continued to thor- Nitrogen was then admitted to the glassreactor and a small pressure was maintained while the polymer wasextruded from the glass reactor in the form of a polymer ribbon. Thepolymer ribbon was subsequentlyi cooled, pelletized, washed and thendried. The polymer was a white solid having a relative viscosity ofabout 55 to 60 as determined by a concentration of 11 grams of polymerin 100 milliliters of 90 percent formic acid at 25C. (ASTMD-789-62T).

The polycaproamide pellets containing the antistatic agent and otheradditives were melted at about 285C. and then melt-extruded underpressure of about 1,500 psig through a l6-orifice spinnerette, each ofthe orifices having a diameter of 0.014 inch, to produce a 250-denierfiber. The fiber was then collected at about 1,000 feet per minute andwas drawn about 3.5 times its extruded length to produce a 70-denieryarn. For convenience, this yarn hereinafter will be called Yarn A. Acontrol yarn containing the antistatic agent but no Yarn A and TechnicalB were woven into conventional plain weave fabrics. The fabrics were cutinto fabric test samples having a width of 3 inches and a length of 9inches. The fabric samples were tested for their antistatic property inaccordance with the general procedure described in the Techinical Manualof the American Association of Textile Chemists and Colorists, 1969edition, Volume 45, at pages 206-207. This test procedure is entitledElectrostatic Clinging of Fabrics: Fabric to Metal Test and is numberedAATCC 115-1969. In accordance with this electrostatic test, Yarn A andYarn B both showed excellent antistatic properties, for example, averagetime for fabric samples to decling from metal completely on their own asabout 120 seconds after 25 wash cycles. Yarn A and Yarn B were alsotested for the number of nubs per pound as shown in Example 5.

EXAMPLE This example outlines the method used for locating, identifyingand calculating the nubs per pound in Yarn A and Yarn B as prepared inExample 4. In this method a nub is defined as an enlarged place in afilament which is no more than several filament diameters in length.This method may be used for either monofilament of multifilament yarns;however, it is not applicable to most types of crimped yarn.

In accordance with the test, the 70-denier yarn is drawn directly fromthe package by means of an air aspirator and is passed through anopening of known width, specifically, 0.0030 inch in width. Such anopening is conveniently provided by use of a ceramic cleaner gap, whichis well-known in the art. The presence of a nub is detected when itstops the yarn passage through the opening. The filaments are separatedand the cause of the yarn stopping identified as a nub or as the twistedend of a broken filament. For representative results, about grams ofyarn is passed through the gap and the number of nubs counted. Table 1below shows the results of testing on Yarn A and Yarn B.

TABLE I Detennination of Nubs Per Pound Yarn Nub Count Per Sample Poundof Yarn Yarn A 1,463 Yarn B 4,257

It will be noted that the addition of only antistatic compound to thepolyamide caused the nub count to increase to 4,257 per pound of yarn,which is much higher than ordinary polyamide fiber. However, theaddition of the anti-static compound plus the phenol compound reducedthe nub count to 1,463 nubs per pound of yarn.

EXAMPLE 6 CH CH COOC 2-I EXAMPLE 7 The procedure of Example 4 (Yarn A)was followed except that grams of the antistatic additive of Example 1was used together with 1.35 grams of tetra[- methylene 3-(3',5di-t-butyl-4'-hydroxyphenyl)propionate]methane and 1.35 grams ofdistearyl thiodipropionate.

The fiber produced was pale yellow and had a nub count of 1,463 nubs perpound of yarn.

EXAMPLE 8 The procedure of Example 4 (Yarn A) was follwed except that 90grams of the antistatic additive of Example 2 was used together with 2.7grams of tetra[methylene 3-( 3 ',5 'di-t-butyl-4f-hydroxyphenyl)propionate]methane. The fiber produced was pale yellow and had a nubcount of 1,487 nubs per pound of yarn. A control containing only theantistatic additive of Example 2 was produced and had a nub count of5,362 nubs per pound'of yarn.

EXAMPLE 9 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 2 was used together with2.7 grams ofoctadecyl-3- (3 ,5 '-di-tertiary butyl-4'-hydroxyphenyl)propionate. The fiber produced was pale yellow and had anub count of 982 nubs per pound of yarn.

EXAMPLE EXAMPLE 1 l The procedure of Example 4 (Yarn A) was followedexcept that 90 grams of the antistatic additive of Example 3 was usedtogether with 2.7 grams of tetra[methylene 3-( 3 ,5'di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,475 nubs per pound ofyarn.

EXAMPLE 12 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 3 was used together with2.7 grams of octadecyl-3- (3 ,5 '-di-tertiary butyl-4 -hydroxyphenyl)propionate. The fiber produced was pale yellow and had a nub count of1,150 nubs per pound of yarn.

EXAMPLE 13 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 3 was used together with1.35 grams of tetra[- methylene3-(3,5.-ditertiary-butyl-4-hydroxyphenyl)- propionate1methane and 1.35grams of distearylthiodipropionate. The fiber produced was pale yellowand had a nub count of 1,418 nubs per pound of yarn.

EXAMPLE 14 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1504 was used together with 3.26 grams of dimethylterephthalate, a molar ratio of l to 0.7.

The antistatic additive produced was a soft solid having a meltviscosity of 1,300 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 15 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1504 was used together with 4.66 grams of dimethylterephthalate, a molar ratio of 1.0.

The antistatic additive produced was a soft solid having a meltviscosity of 17,500 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 16 The procedure of Example 2 was followed except that 300 gramsof Tetronic 1504 was used together with 4.41 grams of the diisocyanatecompound of Example 2, a molar ratio of l to 0.7.

The antistatic additive produced was a soft solid having a meltviscosity of 2, 1 50 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 17 The procedure of Example 2 was followed except that 300 gramsof Tetronic 1504 was used together with 6.3 grams of the diisocyanatecompound of Example 2, a molar ratio of 1.

The antistatic additive produced was a soft solid having a meltviscosity of 17,200 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 18 The procedure of Example 4 (Yarn A) was followed except thatgrams of the antistatic additive of Example 14 was used together with2.7 grams of tetra[- methylene 3( 3 ,5 -di-tertiary-butyl-4-hydroxyphenyl)propionate] methane. The fiber produced was pale yellowand had a nub count of 2,168 nubs per pound of yarn.

A control yarn containing only the antistatic additive of Example 14 wasproduced and had a nub count of 6,000 nubs per pound of yarn.

This example illustrates that antistatic additives having a relativelylow melt viscosity also can be effectively protected from a high nubcount.

EXAMPLE 19 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 15 was used together with2.7 grams of tetra[- methylene 3-(3,5-ditertiary-butyl-4-hydroxyphenyl)-propionatelmethane. The fiber produced was pale yellow and had a nubcount of 1,648 nubs per pound of yarn.

A control yarn containing only the antistatic additive of Example 15 wasproduced and had a nub count of 5,451 nubs per pound of yarn.

EXAMPLE 20 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 17 was used together with2.7 grams of tetra[- methylene3-(3',5"-ditertiary-butyl-4'-hydroxyphenyl)- propionate]methane. Thefiber produced was pale yellow and had a nub count of 2,086 nubs perpound of yarn.

A control yarn containing only the antistatic additive of Example 17 wasproduced and had a nub count of 5,173 nubs per pound of yarn.

EXAMPLE 21 The procedure of Example 1 was followed except that 300 gramsof the Tetronic 1508 (molecular weight 27,000) was used together with1.95 grams of dimethyl terephthalate (a molar ratio of l to 0.9).

The antistatic agent produced was a soft solid having a melt viscosityof 18,360 centipoises at C. measured with a Brookfield viscometer. Theviscosity of the original Tetronic 1508 was 6,400 centipoises at 100C.

EXAMPLE 22 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 21 was used together with2.7 grams of tetra[- methylene 3-( 3 ,5 '-ditertiary-butyl-4'-hydroxyphenyl propionate]methane. The fiber produced was pale yellowand had a nub count of 1,608 nubs per pound of yarn.

A control yarn containing only the antistatic additive of Example 21 wasproduced and had a nub count of 5,771 nubs per pound of yarn.

EXAMPLE 23 The procedure of Example 4 (Yarn A) was followed that 90grams of the antistatic additive of Example 21 was used together with2.7 grams of octadecyl-3-(3 ,5 ditertiarybutyl-4-hydroxyphenyl)propionate. The fiber produced was pale yellow andhad a nub count of 1,287 nubs per pound of yarn.

EXAMPLE 24 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 21 was used together with1.35 grams of the tetra[- methylene 3-( 3 ,5'-ditertiary-butyl-4-hydroxyphenyl)- propionate]methane and 1.35 gramsof the distearylthiodipropionate. The fiber produced was pale yellow andhad a nub count of 1,563 nubs per pound of yarn.

EXAMPLE 25 EXAMPLE 26 The procedure of Example 1 was followed exceptthat 300 grams of Tetronic 901 (molecular weight 4,750) was usedtogether with 11.1 grams of dimethyl terephthalate. The antistaticcompound produced was a soft solid having a melt viscosity of 4,300centipoises at 100C., measured with the Brookfield viscometer. Theviscosity of the original Tetronic 901 was 67 centipoises at 100C.

EXAMPLE 27 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 26 was used together with2.7 grams tetra[methylene 3-(3, '-di-isopropyl4-hydroxyphenyl)propionate]methane. The fiber produced was pale yellowand had a nub count of 1,832 nubs per pound of yarn.

A control yarn was made with only the antistatic additive of Example 26.The yarn had a nub count of 7,315 nubs per pound.

EXAMPLE 28 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 26 was used together with2.7 grams of octadecyl-3-(3'-,5'-di-isopropyl4'-hydroxypheny1)propionate. The fiber produced waspale yellow and had a nub count of 1,371 nubs per pound of yarn.

EXAMPLE 29 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1307 (molecular weight 18,600) was used together withi 2.82grams of dimethylterephthalate (a molar ratio of 1 to 0.9). Theantistatic agent produced was a waxy solid having a melt viscosity of18,700 centipoises at 100C. The viscosity of the original Tetronic 1307at 100C. was 1,220 centipoises.

EXAMPLE 30 The procedure of Example 4 (Yarn A) was followed except thatgrams of the antistatic additive of Example 29 was used together with2.7 grams of tetra[- methylene 3-(3,5-ditertiary-butyl-4-hydroxypheny1)- propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,518 nubs per pound ofyarn.

A control yarn was made wth only the antistatic additive of Example 29and no phenol compound. The yarn had a nub count of 4,560 nubs per poundof yarn.

EXAMPLE 3 l The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 29 was used together with2.7 grams of octadecyl-3- (3,5-di-tertiarybutyl-4'-hydroxyphenyl)propionate. The fiber produced was pale yellowand had a nub count of 1,310 nubs per pound of yarn.

EXAMPLE 32 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 29 was used together with1.35 grams of tetra[- methylene 3-( 3 ,5 -di-tertiary-buty1-4-hydroxyphenyl)propionate]methane and 1.35 grams ofdistearylthiodipropionate. The fiber produced was pale yellow and had anub count of 1,165 nubs per pound of yarn.

EXAMPLE 33 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with0.9 gram of tetra[methylene 3-( 3 ,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,950 nubs per pound ofyarn.

EXAMPLE 34 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with1.8 grams of tetra[methylene3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate] methane. The fiberproduced was pale yellow and had a nub count of 1,720 nubs per pound ofyarn.

EXAMPLE 35 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with3.6 grams of tetra[methylene 3-( 3 ,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,275 nubs per pound ofyarn.

EXAMPLE 36 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with4.5 grams of tetra[methylene 3-( 3 ,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,330 nubs per pound ofyarn.

EXAMPLE 37 -The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with5.4 grams of tetra[methylene 3-( 3 ,5 '-cli-tertiary-butyl-4-hydroxyphenyl)propionate]methane. The fiber produced was pale yellowand had a nub count of 1,682 nubs per pound of yarn.

EXAMPLE 38 The procedure of Example 4 (Yarn A) was followed except that60 grams of the antistatic additive of Example 1 was used together with1.8 grams of tetra[methylene 3-( 3 ,5 '-di-tertiary-butyl-4'-hydroxyphenyl )propionate]methane. The fiber produced was pale yellowand had a nub count of 1,250 nubs per pound of yarn.

A control yarn containing only the antistatic additive was produced andhad a nub count of 3,780 nubs per pound of yarn.

EXAMPLE 39 EXAMPLE 40 The procedure of Example 4 (Yarn A) was followedexcept that 30 grams of the antistatic additive of Example 1 was usedtogether with 0.9 gram of tetra[methylene 3-( 3 ,5 -di-tertiary-butyl-4'-hydroxyphenyl )propionate]methane. The fiber produced was pale yellowand had a nub count of 851 nubs per pound of yarn.

A control yarn containing only the antistatic additive was produced andhad a nub count of 3,365 nubs per pound of yarn.

EXAMPLE 41 The procedure of Example'4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 4 was used together with1.35 grams of octadecyl-3- (3 ,5 '-di-tertiary butyl-4-hydroxyphenyl)propionate and 1.35 grams of distearylthiodipropinate. The fiberproduced was pale yellow and had a nub count of 1,100 nubs per pound ofyarn.

EXAMPLE 42 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example l was used together with0.45 gram of tetra[methy lene i3-(3,5-di-tertiary-butyl-4'-hydroxyphenyl)pro pionate]methane. The fiberproduced was pale yellow and had a nub count of 2,125 nubs per pound ofyarn.

EXAMPLE 43 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example l was used together with7.2 grams of tetra[methylene 3-( 3 ,5 -di-tertiary-butyl-4-hydroxyphenyl )propionate]methane. The fiber produced was pale yellowand had a nub count of 1,650 nubs per pound of yarn.

EXAMPLE 44 Polycaproamide pellets containing the antistatic agent ofExample 1 and tetra[methylene 3-(3',5'-ditertiarybutyl-4 -hydroxyphenyl)propionate methane were prepared in accordance with the procedure ofExample 4(Yarn A). The polycaproamide pellets were melted at about 285C.and the melt extruded under pressure of 15 psig to a orificespinnerette, each of the orifices having a diameter of 0.018 inch toproduce a 4,500 denier fiber. The fiber was collected at 1,000 feet perminute and was drawn about 4 times the extruded length to produce 1,125denier yarn. This yarn is particularly useful in the production ofcarpets as indicated in the following testing procedures.

The yarn was textured using a steam jet and then twopiled. This yarn wastufted into a level loop carpet at 6.5 stitch rate, 9-10/32 inch pileheight, mock dyed and latexed. Static buildup of the carpet was testedby a shuffle test measuring the electrostatic voltage buildup on aperson walking with a series of short shuffiing steps on a piece ofcarpet conditioned at 70F. at 20% relative humidity. The voltagegeneratedwas 4.8 KV.

The untextured yarn was alsotested for nubs using the nub countprocedure of Example 5 except that the ceramic cleaner gap used had anopening of 0.006 inch. The nub count of the yarn was 100, nubsper pound.

A control yarn made with no additives had a nub count of nubs per pound,but carpet made with the control yarn generated a voltage of 14.1 KV inthe above-described shuffle test.

EXAMPLE 45 The procedure of Example 44 was repeated except that thepolycaproamide pellets were made with the antistatic agent of Example 1and octadecyl-3-(3,5- ditertiary butyl-4'-hydroxyphenyl)propionate. Thenub count of the resulting yarn was 102 nubs per pound. Carpet made withthe yarn generated a voltage of 4.9 KV in the above-described shuffletest.

Discussion In additional tests it was determined that the molecularweight of the tetrol compound used to prepare the chainextendedantistatic compound is preferably between about 4,000 and about- 50,000,the ethylene oxide moieties making up about 10 to about of the molecularweight of said compound. Preferably, the antistatic fiber contains fromabout 2 to about 8% of the antistatic compound.

By antistatic" fiber is meant fibers that will pass the cling test andshuffle test is described in US. Pat. No. 3,657,386. By fiber"- is meantmultifilament yarn, monofilament, and all the known physical forms ofsynthetic fibers. By polyamide is meant the polymers made bycondensation of the diamines with dibasic acids or by polymerization oflactams or amino acids, resulting in-a synthetic resin characterized bythe recurring group -CONl-l. By ethylene oxide moiety is meant theportion of the chemical molecule -(Cl-l C- H O).

Desirably, the chain-extended antistatic compound and the otheradditives are substantially uniformly dispersed in the polyamide.Preferably, the sulfur compound is used together with the phenolcompound, and the weight ratio of the phenol compound to sulfur compoundis preferably between 0.25 and 4.0.

EXAMPLE 46 The procedure of Example 4 (Yarn A) was repeated except thatthe additives, i.e., 2.7 grams of the tetra [methylene 3-( 3 ',5-di-tertiary-butyl 4 hydroxyphenyl) propionate]methane and 90 grams ofthe antistatic compound of Example 1 were charged to the glass reactorwith the e-caprolactam and aminocaproic acid. The fiber produced waspale yellow and had a nub count of 1,585 nubs per pound of yarn. Yarnprepared in a similar way containing only the antistatic additivecontained 6,030 nubs per pound of yarn.

EXAMPLE 47 Procedure and additives were similar to Example 4 (Yarn A)except the polyamide was polymerized from poly (hexamethylammoniumadipate salt. A fiber was produced and nubs counted as in Example 5, andthe result was 1,512 nubs per pound of yarn. A second yarn, similarlyprepared with antistatic additive and no additional additive, contained5,625 nubs per pound of yarn. claim:

We claim:

1. In a process for the formation of an antistatic polyamide fiber froma fiber-forming polyamide polymer containing about 1 to 12% by weight ofan antistatic compound which is a chainextended reaction product of atetrol compound represented by the formula:

li (OCi-I CH (OCHCH 3 H(OCrl CH (OCHCH where a, b, c, d, e,f, g, and hare each a whole number and A is a difunctional radical from ahydrocarbon containing 1 to 13 carbon atoms, said tetrol compound havinga molecular weight between about 4,000 and about 50,000 and at least onecompound selected from the group consisting of diepoxides, by extrudingthe molten polymer through an orifice into a quenching medium andthereafter stretching the resulting filaments, the improvementcomprising dissolving in the extrudate prior to extrusion at least 0.1%by weight, based on the weight of the antistatic compound, of a phenolcompound selected from the group consisting of:

(lower) alkyl HO y in which x has a value of from 1 to 6 and y has avalue of from 6 to 30; and

R\ C/ R R R in which R is (lower) alkyl (lower) alkyl wherein x has avalue from 1 to 6 and y has a value of l to 6.

2. The process of claim 1 wherein 0.5 to 8% by weight of the phenolcompound is incorporated into the fiber, based on the weight of theantistatic compound.

3. The process of claim 2 additionally comprising dissolving in theextrudate prior to extrusion at least 0.1% by weight, based on theweight of the antistatic additive, of a sulfur compound of the formula:

(CH CHO) (CH CH O) H CH CI-IO)g (CH2CH O) 1-1 (c n COOR" where R" is analkyl radical containing 8 to 18 carbon atoms and n is l to 3.

4. The process of claim 3 wherein the weight ratio of the phenolcompound to the sulfur compound is between 0.25 and 4.0.

5. The process of claim 4 wherin the phenol compound is selected fromthe group consisting of tetra[- methylene 3-( 3 ,5 -di-tertiary-butyl-4-hydr0xyphenyl)propionate] methane and octadecyl-3-(3',5'- di-tertiarybutyl-4-hydroxyphenyl)propionate.

6. An antistatic fiber consisting essentially of polyamide and about 1to 12% by weight of an antistatic compound which is a chainextendedreaction product of a tetrol compound represented by the formula:

9 H(OCH2CI1IZ)a (ocacn (cn cno) C (cn cn o) H CH \NAN CH3 I 3 I n H (ocncn c (ocncn f (cn cam (cn cn m where a, b, c, d, e,f, g and h are each awhole number and A is a difunctional radical from a hydrocarboncontaining l to 13 carbon atoms, said tetrol compound having a molecularweight between about 4,000 and about 50,000, and at least one compoundselected from the group consisting of diepoxides; and at least 0. 1% byweight, based on the weight of the antistatic compound, of a phenolcompound selected from the group consisting of (lower) alkyl (lowe r)alkyl in which x has a value of from 1 to 6 and y has a value of from 6to 30; and

R a R in which R is 18 (lower) alkyl (lower) alkyl wherein x has a valuefrom 1 to 6 and y has a value of 1 to 6.

7. The fiber of claim 6 wherein 0.5 to 8% by weight of the phenolcompound is incorporated into the fiber based on the weight of theantistatic compound.

8. The fiber of claim 7 additionally consisting of at least 0.1% byweight, based on the weight of the antistatic additive, of a sulfurcompound of the formula:

" (c H coca" \(CPH COOR"

1. IN A PROCESS FOR THE FORMATION OF AN ANTISTATIC POLYAMIDE FIBER FROMA FIBER-FORMING POLYAMIDE POLYMER CONTAINING ABOUT 1 TO 12% BY WEIGHT OFAN ANTISTATIC COMPOUND WHICH IS A CHAINEXTENDED REACTION PRODUCT OF ATETROL COMPOUND REPRESENTED BY THE FORMULA:
 1. In a process for theformation of an antistatic polyamide fiber from a fiber-formingpolyamide polymer containing about 1 to 12% by weight of an antistaticcompound which is a chainextended reaction product of a tetrol compoundrepresented by the formula:
 2. The process of claim 1 wherein 0.5 to 8%by weight of the phenol compound is incorporated into the fiber, basedon the weight of the antistatic compound.
 3. The process of claim 2additionally comprising dissolving in the extrudate prior to extrusionat least 0.1% by weight, based on the weight of the antistatic additive,of a sulfur compound of the formula:
 4. The process of claim 3 whereinthe weight ratio of the phenol compound to the sulfur compound isbetween 0.25 and 4.0.
 5. The process of claim 4 wherin the phenolcompound is selected from the group consisting of tetra(methylene3-(3'',5''-di-tertiary-butyl-4''-hydroxyphenyl)propionate) methane andoctadecyl-3-(3'',5''-di-tertiary butyl-4''-hydroxyphenyl)propionate. 6.An antistatic fiber consisting essentially of polyamide and about 1 to12% by weight of an antistatic compound which is a chainextendedreaction product of a tetrol compound represented by the formula:
 7. Thefiber of claim 6 wherein 0.5 to 8% by weight of the phenol compound isincorporated into the fiber based on the weight of the antistaticcompound.
 8. The fiber of claim 7 additionally consisting of at least0.1% by weight, based on the weight of the antistatic additive, of asulfur compound of the formula:
 9. The fiber of claim 8 wherein theweight ratio of the phenol compound to the sulfur compound is between0.25 and 4.0.